Colorant compositions

ABSTRACT

Disclosed are colorant compounds of the formula  
                 
 
     wherein R, R 1 , R 2 , R 3 , and R 4  each, independently of the others, is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and wherein R, R 1 , R 2 , R 3 , and R 4  each can be joined to a phenyl moiety to form a ring, each R′ a , R′ b , and R′ c , independently of the others, is a halogen atom, an alkyl group, an alkoxy group, a nitrile group, a nitro group, an amide group, or a sulfonamide group, z1, z2, and z3 each, independently of the others, is an integer of 0, 1, 2, 3, or 4, n is an integer representing the number of carbon atoms in each repeat alkylene oxide unit, x is an integer representing the number of repeat alkylene oxide units, D is an anion, and g is the charge on the anion, wherein said colorant has no more than one —OH, —SH, or primary or secondary amino group per molecule.

CROSS-REFERENCES TO COPENDING APPLICATIONS

[0001] Copending application U.S. Ser. No. ______ (not yet assigned;Attorney Docket Number D/A0412), filed concurrently herewith, entitled“Colorant Precursor Compositions,” with the named inventors Jeffery H.

[0002] Banning, Donald R. Titterington, and Clifford R. King, thedisclosure of which is totally incorporated herein by reference,discloses colorant precursor compounds of the formula

[0003] wherein R is an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group, and wherein R can be joined to the phenyl moietyto form a ring, each R′, independently of the others, is a halogen atom,an alkyl group, an alkoxy group, a nitrile group, a nitro group, anamide group, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, and x is an integer representing the numberof repeat alkylene oxide units, wherein said colorant precursor has nomore than one —OH, —SH, or primary or secondary amino group permolecule.

[0004] Copending application U.S. Ser. No. ______ (not yet assigned;Attorney Docket Number D/A0412Q), filed concurrently herewith, entitled“Colorant Compositions,” with the named inventors Jeffery H. Banning,Donald R. Titterington, and Clifford R. King, the disclosure of which istotally incorporated herein by reference, discloses colorant compoundsof the formula

[0005] wherein R is an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group, and wherein R can be joined to the phenyl moietyto form a ring, each R′, independently of the others, is a halogen atom,an alkyl group, an alkoxy group, a nitrile group, a nitro group, anamide group, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, and A and B each, independently of theother, are hydrogen atoms, halogen atoms, tertiary amino groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, ester groups, amide groups, sulfate groups,sulfonate groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, sulfone groups, acyl groups, azo groups, cyanato groups,alkyl groups, alkoxy groups, aryl groups, aryloxy groups, arylalkylgroups, arylalkyloxy groups, alkylaryl groups, or alkylaryloxy groups,wherein said colorant has no more than one —OH, —SH, or primary orsecondary amino group per molecule.

[0006] Copending application U.S. Ser. No. ______ (not yet assigned;Attorney Docket Number D/A0413), filed concurrently herewith, entitled“Colorant Compositions,” with the named inventors Jeffery H. Banning,Donald R. Titterington, and Clifford R. King, the disclosure of which istotally incorporated herein by reference, discloses colorant compositionof the formula

[0007] wherein R is an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group, and wherein R can be joined to the phenyl moietyto form a ring, R′ is an aromatic- or heteroaromatic-containing group,each R_(a), independently of the others, is a halogen atom, an alkylgroup, an alkoxy group, a nitrile group, a nitro group, an amide group,or a sulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is aninteger representing the number of carbon atoms in each repeat alkyleneoxide unit, and x is an integer representing the number of repeatalkylene oxide units, wherein said colorant has no more than one —OH,—SH, or primary or secondary amino group per molecule.

BACKGROUND OF THE INVENTION

[0008] The present invention is directed to specific colorant compoundsand to ink compositions containing these colorant compounds. Morespecifically, the present invention is directed to specifictriarylmethane colorant compounds, and to ink compositions containingthese colorant compounds. One embodiment of the present invention isdirected to a colorant compound of the formula

[0009] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein said colorant has no more than one —OH, —SH, orprimary or secondary amino group per molecule. Another embodiment of thepresent invention is directed to a compound comprising two or moremoieties of the formula

[0010] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein said moieties each contain no —OH groups, —SH groups,or primary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change carrier and a colorant compound comprising oneor more moieties of the formula

[0011] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

[0012] In general, phase change inks (sometimes referred to as “hot meltinks”) are in the solid phase at ambient temperature, but exist in theliquid phase at the elevated operating temperature of an ink jetprinting device. At the jet operating temperature, droplets of liquidink are ejected from the printing device and, when the ink dropletscontact the surface of the recording substrate, either directly or viaan intermediate heated transfer belt or drum, they quickly solidify toform a predetermined pattern of solidified ink drops. Phase change inkshave also been used in other printing technologies, such as gravureprinting, as disclosed in, for example, U.S. Pat. No. 5,496,879 andGerman Patent Publications DE 4205636AL and DE 4205713AL, thedisclosures of each of which are totally incorporated herein byreference.

[0013] Phase change inks for color printing typically comprise a phasechange ink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

[0014] Phase change inks have also been used for applications such aspostal marking, industrial marking, and labelling.

[0015] Phase change inks are desirable for ink jet printers because theyremain in a solid phase at room temperature during shipping, long termstorage, and the like. In addition, the problems associated with nozzleclogging as a result of ink evaporation with liquid ink jet inks arelargely eliminated, thereby improving the reliability of the ink jetprinting. Further, in phase change ink jet printers wherein the inkdroplets are applied directly onto the final recording substrate (forexample, paper, transparency material, and the like), the dropletssolidify immediately upon contact with the substrate, so that migrationof ink along the printing medium is prevented and dot quality isimproved.

[0016] Compositions suitable for use as phase change ink carriercompositions are known. Some representative examples of referencesdisclosing such materials include U.S. Pat. No. 3,653,932, U.S. Pat. No.4,390,369, U.S. Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat.No. 4,851,045, U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S.Pat. No. 5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879,European Patent Publication 0187352, European Patent Publication0206286, German Patent Publication DE 4205636AL, German PatentPublication DE 4205713AL, and PCT Patent Application WO 94/04619, thedisclosures of each of which are totally incorporated herein byreference. Suitable carrier materials can include paraffins,microcrystalline waxes, polyethylene waxes, ester waxes, fatty acids andother waxy materials, fatty amide containing materials, sulfonamidematerials, resinous materials made from different natural sources (talloil rosins and rosin esters, for example), and many synthetic resins,oligomers, polymers, and copolymers.

[0017] U.S. Pat. No. 5,864,002 (Stephens et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses a method ofproviding for manufacturing a colored polymer resin having the steps of:(a) blending a disazo colorant into a mixture of monomers, the coloranthaving a poly(oxyalkylene) substituent comprising from 2 to 200 alkyleneoxide residues, bonded to each end of the disazo chromophore, thepoly(oxyalkylene) substituent having a nucleophilic terminal group whichis capable of reacting with at least a portion of the monomers; (b)providing conditions under which the monomers and disazo colorantpolymerize to form a colored polymer resin.

[0018] U.S. Pat. No. 5,591,833 (Hines et al.), the disclosure of whichis totally incorporated herein by reference, discloses colorants andcompositions useful as a fugitive or permanent colorant for a variety ofsubstrates, or as intermediates for their manufacture, and having one ormore improved properties of enhanced aqueous washability, compatibilitywith and non-extractibility from thermoplastic resins, or reactivitywith resins having reactive functionality, said composition having theformula C(Z)₁₋₈ wherein C is the residue of a reactant having from 1 to8 nucleophilic site residues to which the Z moieties are attached; saidZ moieties containing at least about 60 weight percent ofpoly(oxyalkylene) which comprises (a) at least one glycidol residuesegment of 2 to 6 glycidol residues attached to a nucleophilic site ofC, wherein said poly(oxyalkylene) contains a total of from 2 to 20glycidol residues, (b) and wherein said poly(oxyalkylene) furthercontains the residues of one or more other epoxide reactants of ethyleneoxide (EO), propylene oxide (PO), or butylene oxide (BO), or mixturesthereof, wherein said poly(oxyalkylene) contains a total of from about10 to about 600 of said EO, PO, or BO residues, or mixtures thereof, atleast about 75 mole percent of which are EO residues, (c) and with theprovisions that the ratio of the total of —O—PO— and —O—BO— linkages ofall glycidol residues to the total of all functional oxy linkages ofsaid glycidol residues is less than one, and the molar ratio of EOresidues to glycidol residues is from 4 to 75.

[0019] U.S. Pat. No. 5,290,921 (Moody et al.), the disclosure of whichis totally incorporated herein by reference, discloses primary hydroxylenhanced colorants having markedly improved reactivities in e.g.,polyurethane foams for imparting permanent coloring thereto, thecolorants having the formula C-(Z)¹⁻⁴ wherein C is an azo, methine, orazamethine chromogen and Z is a poly(oxyalkylene) moiety comprising (1)at least two (A) units independently selected from those of the formulae—CH₂CH(O-T)CH₂O— or —CH₂CH(O-T)CH₂O-T and (2) from none to about 200 (B)units of the formula (—RO—) wherein R is straight or branched chainhydrocarbon of 2 to 4 carbons, T is a moiety of the formula—CH₂CH(R₁)—O—(RO)₀₋₄₀—CH₂CH₂OH wherein R₁ is selected from unsubstitutedor substituted alkyl, aryl, alkenyloxyalkyl, alkoxyalkyl, oraryloxyalkyl, and wherein the A units comprise at least 0.5 percent ofthe total A+B units.

[0020] U.S. Pat. No. 5,108,460 (Hines et al.), the disclosure of whichis totally incorporated herein by reference, discloses azo chromophoreshaving polyoxyalkylene substituents that are linked together by acovalent bond or by an intervening connecting group to form dimers ortrimers. The polyoxyalkylene substituents are straight or branched chainpolymers primarily of ethylene oxide which make the dimer and trimercolorants useful as fugitive tints.

[0021] U.S. Pat. No. 5,082,938 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses enhanced branchedchain hydroxyl compounds of formula Y-(Z)₁₋₆ wherein Y is the residue ofa nucleophile devoid of conjugated divalent linking moieties, and each Zis a poly(oxyalkylene) moiety having a molecular weight of from about200 to 10,000 and containing at least one glycidol residue, wherein atleast one of the primary oxy sites of said glycidol residue is linkedpreferably directly to a first epoxide residue of three or more carbons,and wherein said first epoxide residue is linked through a secondary oxysite preferably directly to a second epoxide reside having a primaryterminal hydroxyl.

[0022] U.S. Pat. No. 5,043,013 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses a washableaqueous ink composition having a viscosity of from about 1.0 to about6.0 centipoise and containing from about 10 to about 50 percent byweight of one or more polymeric colorants of the formula

{R₁[(RO)_(a)—Y]_(b)}_(c)

[0023] wherein X is a polar group such as sulfonic acids, sulfonic acidsalts, sulfonamides, sulfonates or the like; R is alkylene; Y is H,alkanoyl, carbamoyl, or the like; R₁ is nitrogen, oxygen, sulfur, or asulfur-containing divalent linking group; a is an integer of from six toabout forty; b and c are each independently selected from one or two; dis an integer of from one to four; the product of (a) (b) (c) is aninteger of from 6 to about 40; and CHROM is a chromophore such as nitro,nitroso, monoazo, disazo and trisazo, diarylmethane, triarylmethane,xanthane, acridine, methine, thiazole, indamine, azine, oxazine, oranthraquinone, wherein the (RO)_(a) moiety is bonded to a carbocyclicaromatic ring of the (CHROM) through R₁.

[0024] U.S. Pat. No. 4,751,254 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses a process forcoloring polyurethane resins during the production of same with reactivecolorants derived from polyalkoxytrifluoroaniline intermediates. Thesecolorants impart increased brightness in shade for both aromatic andheteroaromatic derivatives and increased resistance to stannousoctanoate catalyst over conventional polymeric colorants derived forheteroaromatic compounds. These colorants have the structure

[0025] wherein R₁ is selected from H, a lower alkyl group containingfrom 1 to about 10 carbon atoms, CH₂Cl, CH₂OH, phenyl, or

[0026] where R₆ is H or a lower alkyl group containing from 1 to about 9carbon atoms; R₂ is selected from OH, NH₂, or SH; R₃ is selected from alower alkyl group containing from 1 to about 9 carbon atoms, cyanoalkyl,acetoxyalkyl, or

[0027] where R₁ and R₂ are as given above; R₄ is H, CF₃, a lower alkylgroup containing from 1 to about 9 carbon atoms, Cl, or Br and n is 0 oran integer from 1 to about 125. R₅ is an aromatic or heteroaromaticcontaining group, said colorants being resistant to stannous octanoate,being characterized as having improved brightness and which havefunctionality through reactive substituents thereof.

[0028] U.S. Pat. No. 4,658,064 (Moore et al.), the disclosure of whichis totally incorporated herein by reference, discloses a compound of theformula

[0029] wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ isselected from H or alkyl; Y is a number of from 2 to about 200; and Z isselected from H or

[0030] where W is alkyl.

[0031] U.S. Pat. No. 4,594,454 (Moore et al.), the disclosure of whichis totally incorporated herein by reference, discloses a compound of theformula

[0032] wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ isselected from H or alkyl; Y is a number of from 2 to about 200; and Z isselected from H or

[0033] where W is alkyl.

[0034] U.S. Pat. No. 4,400,320 (Keller et al.), the disclosure of whichis totally incorporated herein by reference, discloses fugitive tintswhich are characterized by the formula

[0035] where R is selected from meta-toluidene, meta-amino phenol,aniline, or dimethoxy aniline, A is selected from N, O, S, or CO₂; thealkylene group of the alkyleneoxy constituent contains from 2 to about 4carbon atoms; n is an integer of from 2 to about 300; m is 1 when A isO, S, or CO₂, and 2 when A is N; x is an integer of from 1 to about 5;and the product of n times m times x (n·m·x) is from 2 to about 400.Also disclosed is a process for preparing alkyleneoxy fugitive tints.

[0036] U.S. Pat. No. 4,284,729 (Cross et al.), the disclosure of whichis totally incorporated herein by reference, discloses a process forcoloring thermosetting resins, made by polyaddition reaction of anucleophile with an electrophile, with a polymeric liquid reactivecoloring agent suitable for incorporation in the resin with theformation of covalent bonds, said coloring agent having the formula

R-(polymeric constituent-X)_(n)

[0037] wherein R is an organic dyestuff radical; the polymericconstituent is selected from polyalkylene oxides and copolymers ofpolyalkylene oxides in which the alkylene moiety of the polymericconstituent contains 2 or more carbon atoms and such polymericconstituent has a molecular weight of from about 44 to about 1500; and nis an integer of from 1 to about 6; and X is selected from —OH, —NH₂,and —SH, said coloring agent being added in an amount sufficient toprovide coloration of said thermosetting resin.

[0038] U.S. Pat. No. 4,132,840 (Hugl et al.), the disclosure of which istotally incorporated herein by reference, discloses polyurethaneplastics that are dyed with dyestuffs of the formula

[0039] wherein R₁ denotes hydrogen, halogen, optionally substitutedC₁-C₄ alkyl, optionally substituted C₁-C₄ alkoxy, and optionallysubstituted C₁-C₄ alkylcarbonylamino and R₂ denotes hydrogen, optionallysubstituted C₁-C₄ alkyl, and optionally substituted C₁-C₄ alkoxy, whileA and B denote optionally branched alkylene chains which can beidentical or different and preferably have 2 to 6 carbon atoms, withformation of covalent bonds, in that the dyestuffs are added before orduring the polyaddition reaction to the reaction mixture of polyol andpolyisocyanate or to one of the components.

[0040] U.S. Pat. No. 3,994,835 (Wolf et al.), the disclosure of which istotally incorporated herein by reference, discloses dispersions ofdyestuffs which contain at least one free amino or hydroxyl groupcapable of reacting with isocyanates under the conditions ofpolyaddition and liquids in which the dyes are soluble to an extent lessthan 2 percent which are suitable for the production of coloredpolyurethane foams. The dye dispersions can be added before or duringthe polyaddition reaction.

[0041] U.S. Pat. No. 5,270,363 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses a colorant fornatural or synthetic resinous or polymeric materials, having the formulaA-[SO₂—N(R₂)—Y]₁₋₄ wherein R₂ is selected for example from hydrogen,methyl, cyclohexyl, phenyl or Y; A is a nonionic metallophthalocyaninechromophore which can be substituted for example with halogen, alkyl,alkoxy, alkylthio, or aryloxy; Y is a poly(oxyalkylene) moietycontaining at least three monomeric units or mixtures thereof of theformula (—RO—) wherein each R is straight or branched alkylene of 1 to 4carbons or mixtures thereof, up to about 20 mole percent of saidmonomeric units may be connected by one or more linking groups such asalkyleneoxy, —NH—, or —NHCONH—, and wherein Y can be terminated byhydrogen, or by at branch substituents, containing 1 to 3 groups ormoieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any ofthe above recited hydrocarbon groups, moieties or substituents maythemselves be substituted with up to four substituents selected, forexample, from alkyl, halogen, mercapto, alkoxycarbonyl, hydroxy, alkoxy,or the like; and wherein each aliphatic hydrocarbon portion or moiety ofthe groups, moieties or substituents recited above contains from 1 to 20carbons.

[0042] U.S. Pat. No. 4,912,203 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses thiophene basedcolorants useful for coloring thermoset resins such as polyurethanesbeing of the formula

[0043] wherein R₁, R₂, and R₃ are selected from halogen, carboxylicacid, alkanoyl, aryloyl, carbocyclic forming polymethylene chains,alkyl, aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl,thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl,amidoaryl, amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, orhydrogen when an adjacent group is isobutyryl; R₄, R₅, and R₇ areselected from hydrogen alkyl, oxyalkyl, sulfonamidoalkyl,sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl,halogen, thioalkyl, and thioaryl; and R₈ and R₉ are selected frompolyalkylene oxide, copolymers of polyalkylene oxides, andhydroxyalkylenes.

[0044] U.S. Pat. No. 4,846,846 (Rekers et al.), the disclosure of whichis totally incorporated herein by reference, discloses a process forcoloring polyurethane resins made by a polyaddition reaction of a polyoland an isocyanate which comprises adding to the reaction mixture beforeor during the polyaddition reaction a reactive coloring agent suitablefor incorporation in the resin with the formation of covalent bonds,said coloring agent having the formula

[0045] in which R₁ and R₂ are independently selected from an alkyl grouphaving from 1 to about 12 carbon atoms, X is —CH₂—, a and a′ areintegers from 1 to about 6, and Y and Y′ are independently selected frompolymeric units of hydroxy alkylenes or alkylene oxide monomers selectedfrom ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide,or glycidol, b and b′ are independently either 0 or 1, and Z and Z′ arereactive groups independently selected from —OH, —NH₂, or —SH.

[0046] U.S. Pat. No. 4,507,407 (Kluger et al.), the disclosure of whichis totally incorporated herein by reference, discloses a process ofcoloring polyurethane resins during the production of same with reactivecolorants having the formula

[0047] wherein R₁, R₂, R₃ are selected from halogen, carboxylic acid,alkanoyl, aryloyl, alkyl, aryl, cyano, sulfonylalkyl, sulfonylaryl,thioalkyl, thioaryl, sulfinylalkyl, sulfinylaryl, dithioalkyl,dithioaryl, thiocyano, amidoalkyl, amidodialkyl, oxydlkyl, oxydryl,hydrogen, sulfonamidoalkyl, sulfonamidoaryl, sulfonamidodialkyl,sulfonamidodiaryl, carbocyclic forming polymethylene chains,sulfenamidoalkyl, sulfenamidodialkyl, sulfenamidoaryl,sulfenamidodiaryl, sulfinamidoalkyl, sulfinamidodialkyl,sulfinamidoaryl, sulfinamidodiaryl; and A is an organic dyestuff couplerthat is resistant to stannous octanoate and flame retardant compoundsand which has functionality through reactive substituents thereof.

[0048] U.S. Pat. No. 5,919,839 (Titterington et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses coloredwaxes made by reacting selected nucleophiles, including alcoholcontaining colorants, with an isocyanate. A phase change ink is made byblending the colored wax with a clear ink carrier composition. The clearink carrier composition can be a fatty amide-based material and/or acombination of isocyanate-derived resins in which the order of additionof the isocyanate and the different nucleophiles can tailor thedistribution of di-urethane, mixed urethane/urea, and/or di-ureamolecules in the final resin product. The colored wax materials areuseful as ingredients with phase change ink carrier compositions to makephase change ink jet inks.

[0049] U.S. Pat. No. 5,456,725 (Bruhnke), the disclosure of which istotally incorporated herein by reference, discloses a process fortemporarily coloring a polyamide substrate whereby a poly(oxyalkylene)substituted methine colorant is applied to the substrate followed byheating the substrate with superheated steam at a temperature of 250° F.or greater, which effectively decolorizes the methine colorant.

[0050] PCT Patent Application WO 97/13816, the disclosure of which istotally incorporated herein by reference, discloses a colored materialsuitable for use in a hot melt ink comprising a oligomeric hot melt inkjet vehicle formed of molecules having a backbone and at least onependant side-chain. A dyestuff is reacted onto the backbone. Thematerial is preferably obtainable as the reaction product of analiphatic or aromatic mono- or di-isocyanate and a hydroxyl groupfunctional dye component, and optionally one or more other suitablematerial. Such suitable materials include mono- and dihydric alcohols,primary and secondary monoamines, functional amides, hydroxyl functionalamines and hydroxyl containing components having a terminal unsaturatedbond.

[0051] “Polymeric Colorants,” J. Miley, IUPAC Pure and AppliedChemistry, Vol. 68, No. 7, p. 1423 (1996), the disclosure of which istotally incorporated herein by reference, discloses specific examples ofpolymeric colorants and how they meet functional requirements.

[0052] While known compositions are suitable for their intendedpurposes, a need remains for improved reactive triarylmethane colorants.In addition, a need remains for reactive triarylmethane colorants thatare easily purified. Further, a need remains for reactive triarylmethanecolorants that exhibit reduced toxicity. Additionally, a need remainsfor reactive triarylmethane colorants that are liquid at roomtemperature. There is also a need for reactive triarylmethane colorantsthat can be tailored for compatibility with various hydrophobic orhydrophilic applications. In addition, there is a need for reactivetriarylmethane colorants that, when reacted with polymers such aspolyurethanes, polyanhydrides, or the like, resist migration and/orsettling. Further, there is a need for reactive triarylmethane colorantsthat, when reacted with other materials, do not result in the formationof products of undesirably high molecular weight. Additionally, there isa need for reactive triarylmethane colorants that, when reacted withother materials, do not result in the formation of products withundesirable crosslinking. A need also remains for reactivetriarylmethane colorants that, when reacted with other materials, formproducts suitable for use in phase change ink compositions. In addition,a need remains for reactive triarylmethane colorants that, when reactedwith other materials, form products that, when incorporated into phasechange ink compositions, exhibit reduced precipitation of the colorantfrom the ink. Further, a need remains for reactive triarylmethanecolorants that, when reacted with other materials, form products that,when incorporated into phase change ink compositions, exhibit reducedclogging of printer heads and resulting printer failure.

SUMMARY OF THE INVENTION

[0053] The present invention is directed to a colorant compound of theformula

[0054] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein said colorant has no more than one —OH, —SH, orprimary or secondary amino group per molecule. Another embodiment of thepresent invention is directed to a compound comprising two or moremoieties of the formula

[0055] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein said moieties each contain no —OH groups, —SH groups,or primary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change carrier and a colorant compound comprising oneor more moieties of the formula

[0056] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

DETAILED DESCRIPTION OF THE INVENTION

[0057] The present invention is directed to a colorant of the formula

[0058] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group (including linear, branched, saturated, unsaturated,cyclic, and unsubstituted alkyl groups, and wherein hetero atoms, suchas oxygen, nitrogen, sulfur, silicon, phosphorus, and the like eithermay or may not be present in the alkyl group), in one embodiment with atleast 1 carbon atom, and in another embodiment with at least about 2carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, an aryl group (including unsubstituted and substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including unsubstituted andsubstituted alkylaryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges,wherein the substituents on the substituted alkyl, aryl, arylalkyl, andalkylaryl groups can be (but are not limited to) halogen atoms, tertiaryamino groups, imine groups, ammonium groups, cyano groups, pyridinegroups, pyridinium groups, ether groups, ester groups, amide groups,sulfate groups, sulfonate groups, sulfide groups, sulfoxide groups,phosphine groups, phosphonium groups, phosphate groups, nitrile groups,mercapto groups, nitro groups, sulfone groups, acyl groups, azo groups,cyanato groups, and the like, as well as mixtures thereof, and whereintwo or more substituents can be joined together to form a ring, each R′,independently of the others, is a halogen atom, an alkyl group, analkoxy group, d nitrile group, a nitro group, an amide group, or asulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit (the alkylene oxide units can each have different numbers of carbonatoms; for example, the polyalkylene oxide chain can comprise a mixtureof repeat ethylene oxide, propylene oxide, and/or butylene oxide units),and typically is from about 2 to about 18, and preferably from about 2to about 4, although the value of n can be outside of these ranges, andx is an integer representing the number of repeat alkylene oxide units,and typically is from about 2 to about 100, and preferably from about 5to about 20, although the value of x can be outside of these ranges,wherein said colorant has no more than one —OH, —SH, or —NHR″ group(i.e., primary or secondary amino group) per molecule, wherein R″ is ahydrogen atom, an alkyl group (including linear, branched, saturated,unsaturated, cyclic, and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in another embodiment withat least about 2 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including unsubstituted and substitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least 5 carbon atoms, and inanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or an alkylaryl group(including unsubstituted and substituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as tolyl or the like, and wherein the substituents onthe substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (butare not limited to) those indicated hereinabove for the R group.

[0059] If desired, various substituents (shown as R′_(a), R′_(b), andR′_(c) groups on the structure) can be present on the central phenylmoiety of the structure to affect the color of a colorant, such as amethine colorant or a triarylmethane colorant, prepared from theprecursor molecule. From 1 to 4 of such substituents can be present oneach phenyl ring, which can be the same as each other or different fromeach other. Examples of such substituents include (but are not limitedto) halogen atoms, such as fluorine, chlorine, bromine, and iodine,alkyl groups, typically with from 1 to about 25 carbon atoms, such asmethyl, ethyl, and the like, alkoxy groups, typically with from 1 toabout 25 carbon atoms, such as methoxy groups, ethoxy groups, and thelike, nitrile groups, nitro groups, amide groups, such as an acetamidogroup or the like, including (but not limited to) those of the generalformula

[0060] wherein R_(a) is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least 1 carbonatom, and in another embodiment with at least about 2 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, and inanother embodiment with no more than about 48 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(including unsubstituted and substituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least 5 carbon atoms, and in another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, such as anacetamido group or the like, sulfonamide groups, including (but notlimited to) those of the formula

[0061] wherein R_(b) is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least 1 carbonatom, and in another embodiment with at least about 2 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, and inanother embodiment with no more than about 48 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(including unsubstituted and substituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least 5 carbon atoms, and in another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, or thelike.

[0062] It should be noted that the R, R₁, R₂, R₃, and R₄ groups caneach, independently of the others, also be joined to one of the centralphenyl moieties to form a ring; for example, compounds of the formulae

[0063] are within the scope of the above formula.

[0064] Materials of this formula can be prepared from a precursor of theformula

[0065] which can be prepared according to the following reaction scheme(in which, for purposes of simplicity, no R′ groups are shown):

[0066] More specifically, the terminal hydroxy group in the polyalkoxyaniline is first converted to an acetate group to protect thisfunctionality in subsequent reaction steps. This conversion can beperformed via an acetylation reaction, wherein the polyalkoxy aniline isfirst heated, typically to a temperature of from about 90 to about 150°C., although the temperature can be outside of this range, and subjectedto vacuum to remove water, and subsequently reacted with aceticanhydride, if desired in the presence of an optional esterificationcatalyst, such as dibutyl tin laurate, para-toluene sulfonic acid,1-methylimidazole, or the like, as well as mixtures thereof, underreflux conditions, typically at a temperature of from about 90 to about150° C., although the temperature can be outside of this range, and aninert atmosphere. The acetic anhydride typically, although notnecessarily, is present in a slight molar excess relative to thepolyalkoxy aniline. Thereafter, excess acetic acid (generated as areaction byproduct) and acetic anhydride can be removed by vacuumdistillation to yield the acetylated product.

[0067] The acetylated product is then admixed with a formylating agent,such as dimethyl formamide, N-methyl formamide (which can be prepared asdisclosed in, for example, Organic Synthesis Collective Volume 3, p 98,1955, John Wiley and Sons, ISBN 0 471 40953 7, the disclosure of whichis totally incorporated herein by reference), or the like, with theformylating agent typically, although not necessarily, present in amolar excess of from about 5 to about 20 percent, and cooled to about 0°C., followed by dropwise addition of POCl₃ in a molar excess amount attemperatures of no more than about 5° C., and subsequent warming to roomtemperature. Thereafter, the reaction mixture is heated, typically to atemperature of from about 50 to about 100° C., although the temperaturecan be outside of this range, and a base, such as sodium hydroxide,potassium hydroxide, calcium hydroxide, calcium oxide, mixtures thereof,or the like is added slowly, with the base typically present in a molarexcess of from about 1.1 moles of base per every one mole of acetylatedproduct to about 10 moles of base per every one mole of acetylatedproduct, although the amount can be outside of these ranges, followed byseparation of the acetylated and formylated product via a separatoryfunnel.

[0068] The acetylated and formylated product is then deprotected toconvert the acetate end group back to a hydroxy group. The acetylatedand formylated product is admixed with a mixture of sodium hydroxide andpotassium hydroxide, with the sodium hydroxide/potassium hydroxidemixture typically present in a molar excess of from about 1.1 moles ofbase per every one mole of acetylated and formylated product to about 10moles of base per every one mole of acetylated and formylated product,although the amount can be outside of these ranges, and heated,typically to a temperature of from about 60 to about 120° C., althoughthe temperature can be outside of these ranges, typically for a periodof about 3 hours, although the time can be greater or lesser than thisamount, followed by addition of water until the cloud point is reached,i.e., when the acetylated and formylated product separates from thewater (typically an amount of water on a molar basis that is from about0.75 to about 3 times as much water as acetylated and formylatedproduct) and continued heating, typically at a temperature of from about60 to about 100° C., although the temperature can be outside of thisrange. The product mixture is then allowed to phase separate, and thedeprotected formylated product can be recovered via a separatory funnel.

[0069] If desired, the cycle of admixing with 0.75 to 3 times as muchwater as product, heating, and separating can be repeated to removesalts to a desired level. If desired, vacuum can be employed for furtherremoval of water from the product.

[0070] Starting materials of the formula

[0071] are commercially available from, for example Henkel Corporation,Mauldin, S.C. For example, a material of this formula wherein n is 2 andx is 10 is available. From the same company is also available as SO-7864a similar material wherein both ethylene oxide and propylene oxidegroups are randomly distributed through the polyalkylene oxide chain inan average molar ratio of about 3.5 moles of ethylene oxide groups to6.5 moles of propylene oxide groups. Materials of this formula can alsobe prepared by, for example, obtaining a commercially available anilineof the formula

[0072] and reacting it with an epoxide compound having the desirednumber of carbon atoms in the presence of a Lewis acid or a base. Morespecifically, if one wants, for example, a compound wherein n is 3(i.e., a polypropylene oxide substituted compound), one can react theaniline with an epoxide compound of the formula

[0073] If one wants a compound wherein n is 2 (i.e., a polyethyleneoxide substituted compound), one can react the aniline with an epoxidecompound of the formula

[0074] The molar ratio of epoxide compound to N-alkyl aniline is suchthat the desired number of repeat alkylene oxide units per N-alkylaniline molecule is obtained; for example, if it is desired to have amolecule with an average of about 10 repeat alkylene oxide units (i.e.,x=10), the molar ratio of epoxide compound to N-alkyl aniline is about10:1.

[0075] The reaction can take place in the presence of a catalyst whichis either a base, such as potassium hydroxide or the like, or a Lewisacid, such as BF₃ etherate or the like. The catalyst is present in anydesired or effective amount, in one embodiment at least about 0.01 moleof catalyst per every one mole of aniline, in another embodiment atleast about 0.05 mole of catalyst per every one mole of aniline, and inyet another embodiment at least about 0.1 mole of catalyst per every onemole of aniline, and in one embodiment no more than about 0.3 mole ofcatalyst per every one mole of aniline, in another embodiment no morethan about 0.2 mole of catalyst per every one mole of aniline, and inyet another embodiment no more than about 0.1 mole of catalyst per everyone mole of aniline, although the relative amounts can be outside ofthese ranges.

[0076] Further information regarding these kinds of reactions isdisclosed in, for example, Preparation I of U.S. Pat. No. 4,091,034,Example 1 of U.S. Pat. No. 4,167,510, Example I of U.S. Pat. No.4,400,320, and Example 1A of U.S. Pat. No. 5,290,921, the disclosures ofeach of which are totally incorporated herein by reference.

[0077] The material of the formula

[0078] is then reacted with one or more suitable aniline compounds toform a triarylmethane colorant. Suitable aniline compounds include thoseof the general formulae

[0079] wherein each R′_(b) and each R′_(c), independently of the other,have the same definitions as R′_(a) and z2 and z3 each, independently ofthe other, have the same definitions as z1, wherein R₁, R₂, R₃, and R₄each, independently of the others, is an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 5 carbon atoms, and in another embodiment with atleast about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, oran alkylaryl group (including unsubstituted and substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the alkyl portion and the aryl portion of thealkylaryl group), in one embodiment with at least about 6 carbon atoms,and in another embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be(but are not limited to) halogen atoms, tertiary amino groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, ester groups, amide groups, sulfate groups,sulfonate groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, sulfone groups, acyl groups, azo groups, cyanato groups,and the like, as well as mixtures thereof, and wherein two or moresubstituents can be joined together to form a ring.

[0080] The reaction takes place by reacting in one embodiment at leastabout 0.9 part by mole, in another embodiment about 0.95 part by mole,and in yet another embodiment about 0.99 part by mole, and in oneembodiment no more than about 1 part by mole of a compound of theformula

[0081] and either from about 2 to about 2.05 parts by mole of a compoundof the formula (in which, for purposes of simplicity, no R′ groups areshown)

[0082] or a mixture of compounds of the formulae (in which, for purposesof simplicity, no R′ groups are shown)

[0083] in any desired relative ratio with respect to each other, whereinthe number of parts by mole of compound containing R₁ and R₂ plus thenumber of parts by mole of compound containing R₃ and R₄ equals fromabout 2 to about 2.05 in the presence of a mineral acid that promotesdehydration, such as sulfuric acid, phosphoric acid, or the like. Themineral acid is present in any desired or effective amount, in oneembodiment at least about 1 mole of mineral acid per every one mole ofcompound of the formula

[0084] and in another embodiment at least about 1.5 moles of mineralacid per every one mole of compound of the formula

[0085] and in one embodiment no more than about 3 moles of mineral acidper every one mole of compound of the formula

[0086] and in another embodiment no more than about 2 moles of mineralacid per every one mole of compound of the formula

[0087] although the relative amounts can be outside of these ranges.

[0088] The reactants are heated to any desired or effective temperature,in one embodiment at least about 70° C., and in another embodiment atleast about 80° C., and in one embodiment no more than about 100° C.,and in another embodiment no more than about 95° C., although thetemperature can be outside of these ranges.

[0089] The reactants are allowed to react for any desired or effectiveperiod of time, in one embodiment at least about 1 hour, and in anotherembodiment at least about 3 hours, and in one embodiment no more thanabout 24 hours, and in another embodiment no more than about 6 hours,although the period of time can be outside of these ranges.

[0090] The reaction proceeds in two steps, as follows (in which, forpurposes of simplicity, no R′ groups are shown):

[0091] Any desired or effective oxidizing agent commonly employed toprepare triarylmethanes can be used, such as chloranil, hydrogenperoxide, benzoquinone, or the like, as well as mixtures thereof. Theoxidizing agent is present in any desired or effective relative amount,in one embodiment at least about 1 mole of oxidizing agent per every onemole of the leuco form of the colorant, and in one embodiment no morethan about 5 moles of oxidizing agent per every one mole of the leucoform of the colorant, and in another embodiment no more than about 2moles of oxidizing agent per every one mole of the leuco form of thecolorant, although the relative amounts can be outside of these ranges.

[0092] The oxidizing agent and the leuco form of the colorant are heatedto any desired or effective temperature, in one embodiment at leastabout 25° C., in another embodiment at least about 55° C., and in yetanother embodiment at least about 100° C., and in one embodiment no morethan about 125° C., in another embodiment no more than about 5° C., andin yet another embodiment no more than about 105° C., although thetemperature can be outside of these ranges.

[0093] The oxidizing agent and the leuco form of the colorant areallowed to react for any desired or effective period of time, in oneembodiment at least about 5 minutes, in another embodiment at leastabout 30 minutes, and in yet another embodiment at least about 60minutes, and in one embodiment no more than about 12 hours, in anotherembodiment no more than about 6 hours, and in yet another embodiment nomore than about 2 hours, although the period of time can be outside ofthese ranges.

[0094] The reaction product mixture can then be neutralized with a base,such as NaOH or the like, and the salt layer can then be separated fromthe product layer. Optionally, the colorant can be subsequently washedwith more water to reduce the salt layer to the level desired.

[0095] The resulting triarylmethane colorant is of the formula

[0096] wherein each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n, and x are as defined hereinabove, D is an anion correspondingto the mineral acid used in the reaction to synthesize the colorant, andg represents the charge on the anion, typically being 1, 2, 3, 4, or thelike.

[0097] Colorants of the present invention can be reacted with variousatoms, groups of atoms, monomers, oligomers, or polymers to form variouscolored monomers, oligomers, or polymers having covalently bondedthereto a colorant according to the present invention. Anotherembodiment of the present invention is directed to a compound comprisingtwo or more moieties of the formula

[0098] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form d ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein said moieties each contain no —OH groups, —SH groups,or primary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer.

[0099] Examples of colored groups of atoms, monomers, oligomers, orpolymers which can be prepared with the colorants of the presentinvention include urethane isocyanate-derived monomers, oligomers, orpolymers, urea isocyanate-derived monomers, oligomers, or polymers,urethane/urea isocyanate-derived monomers, oligomers, or polymers,anhydride monomers, oligomers, or polymers, such as styrene-maleicanhydride monomers, oligomers, or polymers, ester/polyester monomers,oligomers, or polymers, carbonate/polycarbonate monomers, oligomers, orpolymers, and the like. Colored urethane isocyanate-derived monomers,oligomers, or polymers, urea isocyanate-derived monomers, oligomers, orpolymers, and urethane/urea isocyanate-derived monomers, oligomers, orpolymers having covalently bonded thereto a colorant according to thepresent invention are generally the reaction product of a colorantaccording to the present invention and an isocyanate. Colored urethaneisocyanate-derived monomers, oligomers, or polymers, ureaisocyanate-derived monomers, oligomers, or polymers, and urethane/ureaisocyanate-derived monomers, oligomers, or polymers having covalentlybonded thereto a colorant according to the present invention can beprepared by, for example, processes such as those disclosed in U.S. Pat.No. 5,919,839; U.S. Pat. No. 3,994,835; U.S. Pat. No. 4,132,840; U.S.Pat. No. 4,751,254; U.S. Pat. No. 5,290,921; U.S. Pat. No. 5,270,363;U.S. Pat. No. 4,912,203; U.S. Pat. No. 4,846,846; U.S. Pat. No.4,507,407; U.S. Pat. No. 4,284,729; U.S. Pat. No. 5,864,002; PCT PatentApplication WO 97/13816; J. H. Saunders and K. C. Frisch's“Polyurethanes Part I, Chemistry” published by Interscience of New York,N.Y. in 1962; and Olin Chemicals' Luxate® IM isophorone diisocyanatetechnical product information sheet; the disclosures of each of whichare totally incorporated herein by reference. Further information onisocyanate-derived resins is disclosed in, for example, U.S. Pat. No.5,782,966; U.S. Pat. No. 5,750,604; U.S. Pat. No. 5,827,918; U.S. Pat.No. 5,830,942; U.S. Pat. No. 5,994,453; U.S. Pat. No. 6,180,692; U.S.Pat. No. 6,018,005; U.S. Pat. No. 6,028,138; U.S. Pat. No. 6,048,925;U.S. Pat. No. 6,057,399; and U.S. Pat. No. 5,783,658; the disclosures ofeach of which are totally incorporated herein by reference.

[0100] For example, a monoisocyanate reacts with an alcohol to form aurethane as follows:

[0101] Diisocyanates react similarly; for example, isophoronediisocyanate reacts with two moles of alcohol to form a diurethane asfollows:

[0102] Monomeric, oligomeric, and polymeric materials can be preparedwhen HO—R_(b) is a colorant or colorant precursor according to thepresent invention.

[0103] Examples of suitable isocyanates include monoisocyanates,diisocyanates, triisocyanates, copolymers of a diisocyanate, copolymersof a triisocyanate, polyisocyanates (having more than three isocyanatefunctional groups), and the like, as well as mixtures thereof. Examplesof monoisocyanates include octadecylisocyanate; hexadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and para-tolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like, as well as mixtures thereof.Examples of diisocyanates include isophorone diisocyanate (IPDI);toluene diisocyanate (TDI); diphenylmethane-4,4′-diisocyanate (MDI);hydrogenated diphenylmethane-4,4′-diisocyanate (H12MDI); tetra-methylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; dimer diisocyanate and cyclohexylenediisocyanate and its isomers; uretidione dimers of HDI; and the like, aswell as mixtures thereof. Examples of triisocyanates or theirequivalents include the trimethylolpropane trimer of TDI, and the like,isocyanurate trimers of TDI, HDI, IPDI, and the like, and biuret trimersof TDI, HDI, IPDI, and the like, as well as mixtures thereof. Examplesof higher isocyanate functionalities include copolymers of TDI/HDI, andthe like, and MDI oligomers, as well as mixtures thereof.

[0104] Any suitable reaction condition for making urethane compounds bycondensing alcohols with isocyanates can be used to prepare polymericcolorants according to the present invention. Typically (although notnecessarily), the reaction is carried out at elevated temperatures (forexample, from about 60 to about 160° C.) in the presence of an optionalurethane reaction catalyst, such as dibutyl tindilaurate, bismuthtris-neodecanoate, cobalt benzoate, lithium acetate, stannous octoate,triethylamine, or the like. In a specific embodiment, the reactionconditions are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable gases, to prevent oxidizing or yellowingof the reaction products and to prevent undesirable side reactions. Thereaction can employ an inert solvent, such as toluene or the like, orcan be performed neat (i.e., without a solvent). The mole ratio ofreactants is adjusted so that the isocyanate functionalities arecompletely consumed in the reaction with a slight molar excess ofalcohol-substituted or amine-substituted antioxidant typicallyremaining. The reactants can be added together in any order and/or addedto the reaction as physical mixtures. See, for example, J. H. Saundersand K. C. Frisch's “Polyurethanes Part I, Chemistry” published byInterscience of New York, N.Y. in 1962 and Olin Chemicals' LUXATE® IMisophorone diisocyanate technical product information sheet, thedisclosures of each of which are totally incorporated herein byreference, which provide further explanation of this chemistry.

[0105] Colored anhydride resins having covalently bonded thereto acolorant according to the present invention are generally the reactionproduct of a monomeric colorant according to the present invention andan anhydride. Colored anhydride resins having covalently bonded theretoa colorant according to the present invention can be prepared asdisclosed in, for example, U.S. Pat. No. 6,110,264 and U.S. Pat. No.6,322,624, the disclosures of each of which are totally incorporatedherein by reference. Examples of suitable anhydrides include cyclicanhydrides, such as alkylsuccinic anhydrides, alkenylsuccinicanhydrides, and the like, as well as mixtures thereof. Specific examplesinclude (but are not limited to) maleic anhydride, 2,3-diphenylmaleicanhydride, trimellitic anhydride, 2-phenylglutaric anhydride,homophthalic anhydride, isatoic anhydride, n-methylisatoic anhydride,5-chloroisatoic anhydride, phthalic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 4-methylphthalic anhydride,4,4′-(hexafluoroisopropylidine)-diphthalic anhydride,3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,tetrachlorophthalic anhydride, tetrabromophthalic anhydride,3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,3-nitrophthalic anhydride, 4-nitrophthalic anhydride,1,2,4,5-benzenetetracarboxylic dianhydride, diphenic anhydride,1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic anhydride,4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride,3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride,4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride dipotassiumsalt, 1,4,5,8-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylic dianhydride,cis-1,2,3,6-tetrahydrophthalic anhydride,cis-5-norbornene-endo-2,3dicarboxylic anhydride,endo-bicyco[2,2,2]oct-5-ene-2,3dicarboxylic anhydride, cantharidin,methyl-5-norbornene-2,3-dicarboxylic anhydride,exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, citraconicanhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylicanhydride, 3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,dichloromaleic anhydride,1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric anhydride,2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride,3-ethyl-3-methylglutaric anhydride, 3,3tetramethyleneglutaric anhydride,hexafluoroglutaric anhydride, 3,5-diacetyltetrahydropyran-2,4,6-trione,ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaaceticdianhydride, diglycolic anhydride, succinic anhydride, methylsuccinicanhydride, 2,2-dimethylsuccinic anhydride, isobuteneylsuccinicanhydride, 2-octen-1-ylsuccinic anhydride, octadecenylsuccinicanhydride, 3-oxabicyclo[3,1,0]hexane-2,4-dione,cis-1,2-cyclohexanedicarboxylic anhydride,trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalicanhydride, itaconic anhydride, 2-dodecen-1-ylsuccinic anhydride, and thelike, as well as mixtures thereof. For example, colored styrene-maleicanhydride resins having covalently bonded thereto a colorant accordingto the present invention are generally the reaction product of amonomeric colorant according to the present invention and styrene-maleicanhydride. Copolymers of anhydrides with styrene, butadiene,methoxyvinylether, ethylene, alpha-olefins, mixtures thereof, and thelike, are all suitable examples of polymeric materials with which themonomeric colorants of the present invention can be reacted to formcolored polymeric materials. Specific examples of suitable copolymersinclude (but are not limited to) poly(methyl vinyl ether-maleic acid),poly(acrylic acid-co-maleic acid), poly(vinylchloride-co-vinyl-acetate-co-maleic acid), poly(ethylene-maleicanhydride), poly(maleic anhydride-1-octadecene), poly(styrene-co-maleicanhydride), poly(methyl vinyl ether-maleic anhydride),poly(ethylene-co-ethyl acrylate-co-maleic anhydride),poly(ethylene-co-vinyl acetate)-graft-maleic anhydride,polyethylene-graft-maleic anhydride, polypropylene-graft-maleicanhydride, and the like, as well as mixtures thereof.

[0106] The monomeric precursor compounds and colorant compounds of thepresent invention, i.e., those containing only one moiety of the formula

[0107] have no more than one —OH, —SH, or —NHR″ group per molecule,wherein R″ is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, or an alkylaryl group. By this it is meant that, forexample, if the molecule has one —OH group, it has no —SH groups, no—NHR″ groups, and no additional —OH groups. Because the colorantcompounds of the present invention have one and only one of thesegroups, in some embodiments of the invention various advantages can beachieved. For example, when these colorants are reacted with othermaterials to form colored resins, there is no formation of products ofundesirably high molecular weight and no undesired crosslinking. Someadvantages are particularly desirable for phase change ink applications.For example, when these colorants are reacted with other materials toform colored resins and when these colored resins are incorporated intoa phase change ink, precipitation of the colorant from the ink isreduced; more specifically, when multifunctional colorants, rather thatthe chain terminating colorants of the present invention, are employedin reactions of di- or tri-isocyanates and monohydric alcoholic species,some higher molecular weight species are produced which can be insolublein the ink base, often resulting or being manifested as a precipitate inthe prepared material and/or the final ink. In addition, when thesecolorants are reacted with other materials to form colored resins andwhen these colored resins are incorporated into a phase change ink,clogging of printheads and the printer failure accompanying suchclogging can be reduced.

[0108] The present invention is also directed to phase change inks.Another embodiment of the present invention is directed to a phasechange ink comprising a phase change carrier and a colorant compoundcomprising one or more moieties of the formula

[0109] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenylmoiety to form a ring, each R′_(a), R′_(b), and R′_(c), independently ofthe others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group,z1, z2, and z3 each, independently of the others, is an integer of 0, 1,2, 3, or 4, n is an integer representing the number of carbon atoms ineach repeat alkylene oxide unit, x is an integer representing the numberof repeat alkylene oxide units, D is an anion, and g is the charge onthe anion, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups. When onemoiety is present, the group is generally terminated by a hydrogen atomso that the polyalkyleneoxy chain has a terminal hydroxy group. When twoor more moieties are present, said moieties are linked by a central atomor group of atoms or bonded to a polymer.

[0110] In the direct printing mode, the phase change carrier compositionin one embodiment contains one or more materials that enable the phasechange ink (1) to be applied in a thin film of uniform thickness on thefinal recording substrate (such as paper, transparency material, and thelike) when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

[0111] In an offset printing transfer or indirect printing mode, thephase change carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

[0112] When the phase change ink of the present invention comprises acolored oligomer or polymer to which colorant molecules of the presentinvention are covalently bonded, this colored oligomer or polymer canfunction as the sole ink carrier. In addition, such a colored oligomeror polymer can be present in combination with another phase change inkcarrier composition. Further, when the phase change ink of the presentinvention comprises a colorant of the present invention having only onemoiety of the formula

[0113] the colorant is generally present in combination with a phasechange ink carrier composition. Any desired or effective carriercomposition can be used. Examples of suitable ink carrier materialsinclude fatty amides, such as monoamides, tetraamides, mixtures thereof,and the like. Specific examples of suitable fatty amide ink carriermaterials include stearyl stearamide, a dimer acid based tetra-amidethat is the reaction product of dimer acid, ethylene diamine, andstearic acid, a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and a carboxylic acid having atleast about 36 carbon atoms, and the like, as well as mixtures thereof.When the fatty amide ink carrier is a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, the carboxylicacid is of the general formula

[0114] wherein R is an alkyl group, including linear, branched,saturated, unsaturated, and cyclic alkyl groups, said alkyl group in oneembodiment having at least about 36 carbon atoms, in another embodimenthaving at least about 40 carbon atoms, said alkyl group in oneembodiment having no more than about 200 carbon atoms, in anotherembodiment having no more than about 150 carbon atoms, and in yetanother embodiment having no more than about 100 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges. Carboxylicacids of this formula are commercially available from, for example,Baker Petrolite, Tulsa, Okla., and can also be prepared as described inExample 1 of U.S. Pat. No. 6,174,937, the disclosure of which is totallyincorporated herein by reference. Further information on fatty amidecarrier materials is disclosed in, for example, U.S. Pat. No. 4,889,560,U.S. Pat. No. 4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No.4,830,671, U.S. Pat. No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat.No. 5,597,856, U.S. Pat. No. 6,174,937, and British Patent GB 2 238 792,the disclosures of each of which are totally incorporated herein byreference.

[0115] Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO96/14364, PCT Publication WO 97/33943, andPCT Publication WO95/04760, the disclosures of each of which are totallyincorporated herein by reference.

[0116] Mixtures of fatty amide materials and isocyanate-derivedmaterials can also be employed as the ink carrier composition for inksof the present invention.

[0117] Additional suitable phase change ink carrier materials for thepresent invention include paraffins, microcrystalline waxes,polyethylene waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides and other waxy materials, sulfonamide materials,resinous materials made from different natural sources (such as, forexample, tall oil rosins and rosin esters), and many synthetic resins,oligomers, polymers and copolymers, such as ethylene/vinyl acetatecopolymers, ethylene/acrylic acid copolymers, ethylene/vinylacetate/acrylic acid copolymers, copolymers of acrylic acid withpolyamides, and the like, ionomers, and the like, as well as mixturesthereof. One or more of these materials can also be employed in amixture with a fatty amide material and/or an isocyanate-derivedmaterial.

[0118] In one specific embodiment, the phase change ink carriercomprises the ink carrier comprises (a) a polyethylene wax, present inthe ink in an amount in one embodiment of at least about 25 percent byweight of the ink, in another embodiment of at least about 30 percent byweight of the ink, and in yet another embodiment of at least about 37percent by weight of the ink, and in one embodiment of no more thanabout 60 percent by weight of the ink, in another embodiment of no morethan about 53 percent by weight of the ink, and in yet anotherembodiment of no more than about 48 percent by weight of the ink,although the amount can be outside of these ranges; (b) a stearylstearamide wax, present in the ink in an amount in one embodiment of atleast about 8 percent by weight of the ink, in another embodiment of atleast about 10 percent by weight of the ink, and in yet anotherembodiment of at least about 12 percent by weight of the ink, and in oneembodiment of no more than about 32 percent by weight of the ink, inanother embodiment of no more than about 28 percent by weight of theink, and in yet another embodiment of no more than about 25 percent byweight of the ink, although the amount can be outside of these ranges;(c) a dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and a carboxylic acid derivative of a long chainalcohol having greater than thirty six carbon atoms, present in the inkin an amount in one embodiment of at least about 10 percent by weight ofthe ink, in another embodiment of at least about 13 percent by weight ofthe ink, and in yet another embodiment of at least about 16 percent byweight of the ink, and in one embodiment of no more than about 32percent by weight of the ink, in another embodiment of no more thanabout 27 percent by weight of the ink, and in yet another embodiment ofno more than about 22 percent by weight of the ink, although the amountcan be outside of these ranges; (d) a urethane resin derived from thereaction of two equivalents of hydroabietyl alcohol and one equivalentof isophorone diisocyanate, present in the ink in an amount in oneembodiment of at least about 6 percent by weight of the ink, in anotherembodiment of at least about 8 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 16 percent by weight of theink, in another embodiment of no more than about 14 percent by weight ofthe ink, and in yet another embodiment of no more than about 12 percentby weight of the ink, although the amount can be outside of theseranges; (e) a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, present in the ink inan amount in one embodiment of at least about 2 percent by weight of theink, in another embodiment of at least about 3 percent by weight of theink, and in yet another embodiment of at least about 4.5 percent byweight of the ink, and in one embodiment of no more than about 13percent by weight of the ink, in another embodiment of no more thanabout 10 percent by weight of the ink, and in yet another embodiment ofno more than about 7.5 percent by weight of the ink, although the amountcan be outside of these ranges; and (f) an antioxidant, present in theink in an amount in one embodiment of at least about 0.01 percent byweight of the ink, in another embodiment of at least about 0.05 percentby weight of the ink, and in yet another embodiment of at least about0.1 percent by weight of the ink, and in one embodiment of no more thanabout 1 percent by weight of the ink, in another embodiment of no morethan about 0.5 percent by weight of the ink, and in yet anotherembodiment of no more than about 0.3 percent by weight of the ink,although the amount can be outside of these ranges.

[0119] The ink carrier is present in the phase change ink of the presentinvention in any desired or effective amount, in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 50 percent by weight of the ink, and in yet anotherembodiment of at least about 90 percent by weight of the ink, and in oneembodiment of no more than about 99 percent by weight of the ink, inanother embodiment of no more than about 98 percent by weight of theink, and in yet another embodiment of no more than about 95 percent byweight of the ink, although the amount can be outside of these ranges.

[0120] The phase change inks of the present invention contain a colorantcompound comprising one or more moieties of the formula

[0121] wherein R, R₁, R₂, R₃, and R₄ each, independently of the others,is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup as further defined hereinabove, and wherein R, R₁, R₂, R₃, and R₄each can be joined to a phenyl moiety to form a ring, each R′_(a),R′_(b), and R′_(c), independently of the others, is a halogen atom, analkyl group, an alkoxy group, a nitrile group, a nitro group, an amidegroup, or a sulfonamide group as further defined hereinabove, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit as further defined hereinabove, x is aninteger representing the number of repeat alkylene oxide units asfurther defined hereinabove, D is an anion as further definedhereinabove, and g is the charge on the anion, wherein, when thecolorant compound contains exactly one of the moieties, the moietycontains no more than one —OH, —SH, or primary or secondary amino groupper molecule, and when the colorant compound contains more than one ofthe moieties, said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups. This colorant is present in the inkin any desired or effective amount to obtain the desired color or hue,in one embodiment of at least about 1 percent by weight of the ink, inanother embodiment of at least about 2 percent by weight of the ink, andin yet another embodiment of at least about 3 percent by weight of theink, and in one embodiment of no more than about 20 percent by weight ofthe ink, in another embodiment of no more than about 13 percent byweight of the ink, and in yet another embodiment of no more than about 6percent by weight of the ink, although the amount can be outside ofthese ranges. The colorant according to the present invention can eitherbe the sole colorant in the ink or can be present in combination withother colorants, such as dyes, pigments, mixtures thereof, and the like.

[0122] The inks of the present invention can also optionally contain anantioxidant. The optional antioxidants of the ink compositions protectthe images from oxidation and also protect the ink components fromoxidation during the heating portion of the ink preparation process.Specific examples of suitable antioxidants include NAUGUARD® 524,NAUGUARD® 76, and NAUGUARD® 512, commercially available from UniroyalChemical Company, Oxford, Conn., IRGANOX® 1010, commercially availablefrom Ciba Geigy, and the like. When present, the optional antioxidant ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.01 percent by weight of the ink, in anotherembodiment of at least about 0.1 percent by weight of the ink, and inyet another embodiment of at least about 1 percent by weight of the ink,and in one embodiment of no more than about 20 percent by weight of theink, in another embodiment of no more than about 5 percent by weight ofthe ink, and in yet another embodiment of no more than about 3 percentby weight of the ink, although the amount can be outside of theseranges.

[0123] The inks of the present invention can also optionally contain aviscosity modifier. Examples of suitable viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional viscosity modifier is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 15 percent by weight of the ink,although the amount can be outside of these ranges.

[0124] Other optional additives to the inks include clarifiers, such asUNION CAMP® X37-523-235 (commercially available from Union Camp), in anamount in one embodiment of at least about 0.01 percent by weight of theink, in another embodiment of at least about 0.1 percent by weight ofthe ink, and in yet another embodiment of at least about 5 percent byweight of the ink, and in one embodiment of no more than about 98percent by weight of the ink, in another embodiment of no more thanabout 50 percent by weight of the ink, and in yet another embodiment ofno more than about 10 percent by weight of the ink, although the amountcan be outside of these ranges, tackifiers, such as FORAL® 85, aglycerol ester of hydrogenated abietic (rosin) acid (commerciallyavailable from Hercules), FORAL® 105, a pentaerythritol ester ofhydroabietic (rosin) acid (commercially available from Hercules),CELLOLYN® 21, a hydroabietic (rosin) alcohol ester of phthalic acid(commercially available from Hercules), ARAKAWA KE-311 Resin, atriglyceride of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink, in another embodiment of at least about 5 percentby weight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 98 percent by weight of the ink, in another embodiment of no morethan about 75 percent by weight of the ink, and in yet anotherembodiment of no more than about 50 percent by weight of the ink,although the amount can be outside of these range, adhesives, such asVERSAMID® 757, 759, or 744 (commercially available from Henkel), in anamount in one embodiment of at least about 0.1 percent by weight of theink, in another embodiment of at least about 1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, plasticizers, such as UNIPLEX® 250(commercially available from Uniplex), the phthalate ester plasticizerscommercially available from Monsanto under the trade name SANTICIZER®,such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate(SANTICIZER® 278), triphenyl phosphate (commercially available fromMonsanto), KP-140®, a tributoxyethyl phosphate (commercially availablefrom FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 2percent by weight of the ink, and in one embodiment of no more thanabout 50 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 10 percent by weight of the ink,although the amount can be outside of these ranges, and the like.

[0125] The ink compositions of the present invention in one embodimenthave melting points of no lower than about 50° C., in another embodimentof no lower than about 70° C., and in yet another embodiment of no lowerthan about 80° C., and have melting points in one embodiment of nohigher than about 160° C., in another embodiment of no higher than about140° C., and in yet another embodiment of no higher than about 100° C.,although the melting point can be outside of these ranges.

[0126] The ink compositions of the present invention generally have meltviscosities at the jetting temperature (in one embodiment no lower thanabout 75° C., in another embodiment no lower than about 100° C., and inyet another embodiment no lower than about 120° C., and in oneembodiment no higher than about 180° C., and in another embodiment nohigher than about 150° C., although the jetting temperature can beoutside of these ranges) in one embodiment of no more than about 30centipoise, in another embodiment of no more than about 20 centipoise,and in yet another embodiment of no more than about 15 centipoise, andin one embodiment of no less than about 2 centipoise, in anotherembodiment of no less than about 5 centipoise, and in yet anotherembodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

[0127] The ink compositions of the present invention can be prepared byany desired or suitable method. For example, the ink ingredients can bemixed together, followed by heating, to a temperature in one embodimentof at least about 100° C., and in one embodiment of no more than about140° C., although the temperature can be outside of these ranges, andstirring until a homogeneous ink composition is obtained, followed bycooling the ink to ambient temperature (typically from about 20 to about25° C.). The inks of the present invention are solid at ambienttemperature.

[0128] The inks of the present invention can be employed in apparatusfor direct printing ink jet processes and in indirect (offset) printingink jet applications. Another embodiment of the present invention isdirected to a process which comprises incorporating an ink of thepresent invention into an ink jet printing apparatus, melting the ink,and causing droplets of the melted ink to be ejected in an imagewisepattern onto a recording substrate. A direct printing process is alsodisclosed in, for example, U.S. Pat. No. 5,195,430, the disclosure ofwhich is totally incorporated herein by reference. Yet anotherembodiment of the present invention is directed to a process whichcomprises incorporating an ink of the present invention into an ink jetprinting apparatus, melting the ink, causing droplets of the melted inkto be ejected in an imagewise pattern onto an intermediate transfermember, and transferring the ink in the imagewise pattern from theintermediate transfer member to a final recording substrate. An offsetor indirect printing process is also disclosed in, for example, U.S.Pat. No. 5,389,958, the disclosure of which is totally incorporatedherein by reference. In one specific embodiment, the printing apparatusemploys a piezoelectric printing process wherein droplets of the ink arecaused to be ejected in imagewise pattern by oscillations ofpiezoelectric vibrating elements. Inks of the present invention can alsobe employed in other hot melt printing processes, such as hot meltacoustic ink jet printing, hot melt thermal ink jet printing, hot meltcontinuous stream or deflection ink jet printing, and the like. Phasechange inks of the present invention can also be used in printingprocesses other than hot melt ink jet printing processes.

[0129] Any suitable substrate or recording sheet can be employed,including plain papers such as XEROX® 4024 papers, XEROX® Image Seriespapers, Courtland 4024 DP paper, ruled notebook paper, bond paper,silica coated papers such as Sharp Company silica coated paper, JuJopaper, Hammermill Laserprint Paper, and the like, transparencymaterials, fabrics, textile products, plastics, polymeric films,inorganic substrates such as metals and wood, and the like.

[0130] Specific embodiments of the invention will now be described indetail. These examples are intended to be illustrative, and theinvention is not limited to the materials, conditions, or processparameters set forth in these embodiments. All parts and percentages areby weight unless otherwise indicated.

EXAMPLE I Phase Separation of N-Ethyl Aniline Ethoxylate

[0131] To a 100 milliliter beaker equipped with a magnetic stirrer wasadded about 50 milliliters of POE(10) N-ethyl aniline, of the formula

[0132] (obtained from Henkel Corp, Mauldin, S.C.) and about 65milliliters of deionized water. The mixture was placed on a magneticstirring hot plate and stirring and heating were initiated. When thetemperature reached 90° C., the beaker was removed from heat andstirring and was allowed to cool slowly. After several minutes,separation of layers began to occur, and after about 2 hours, thetemperature had returned to room temperature and the separation wascomplete. A separation of the two layers was visually observed, andseparation of the layers was performed with a separatory funnel.

Acetylation/Protection

[0133] To a 1,000 milliliter flask equipped with a vacuum adapter andmagnetic stirrer was added about 400.0 grams of POE(10) N-ethyl aniline.The flask was placed in a 140° C. oil bath under vacuum with stirringfor about 1 hour. The vacuum source was then removed and about 88.3milliliters of acetic anhydride (obtained from Aldrich Chemical Co.,Milwaukee, Wis.) and 10 drops of 1-methylimidazole (obtained fromAldrich Chemical Co.) were added to the flask. A nitrogen atmosphere andreflux condenser were then introduced, and the mixture was allowed toheat at 140 to 150° C. for about 4 hours. Thereafter, the condenser andnitrogen atmosphere were removed and a vacuum was gradually applied withthe temperature at about 130° C. to remove excess acetic anhydride andacetic acid (generated as a reaction byproduct). Infrared spectroscopyshowed that the OH band (3200-3600 cm⁻¹) in the POE(10) N-ethyl anilinehad disappeared in the product, and a carbonyl band (1720-1770 cm⁻¹) hadappeared in the product, indicating the success of the acetylationreaction.

Formylation

[0134] The acetylated product thus formed was transferred to a 1,000milliliter 4-necked flask equipped with a Trubore stirrer, constantpressure addition funnel, nitrogen atmosphere, and thermometer. About128.0 grams of dimethyl formamide (obtained from Aldrich Chemical Co.)was added to the acetylated product, stirring was initiated, and themixture was cooled to about 0° C. About 160.0 grams of POCl₃ (obtainedfrom Aldrich Chemical Co.) were added to the addition funnel and addeddropwise to the reaction mixture at a rate to keep the temperature below5° C. (about 5 hours). The reaction mixture was then stirred for 1additional hour at 5° C., set at room temperature overnight, and thenheated to 80° C. for about 2 hours. Thereafter, about 500 grams of 50percent sodium hydroxide (solid material obtained from Aldrich ChemicalCo.) in water was added slowly at a rate to keep the temperature below80° C. Upon addition of all of the sodium hydroxide solution, themixture was poured into a 1,000 milliliter separatory funnel and allowedto phase separate. The bottom layer (comprising salt and water) was thendrained and discarded.

Deacetylation/Deprotection

[0135] The acetylated and formylated product thus formed was thentransferred back into a 1,000 milliliter 4-necked flask equipped with aTrubore stirrer, nitrogen atmosphere, and thermocouple temperaturecontroller. About 280 grams of 50 percent sodium hydroxide (obtainedfrom Aldrich Chemical Co.) in water and about 90 grams of 50 percentpotassium hydroxide in water (solid material obtained from AldrichChemical Co.) were added, and the reaction mixture was heated to 100° C.and maintained at that temperature for about 3 hours. Thereafter, about72 grams of 50 percent potassium hydroxide (obtained from AldrichChemical Co.) in water and 600 grams of deionized water were added, andheating was continued at 100° C. for an additional hour. The productmixture was then poured into a 2,000 milliliter separatory funnel andallowed to phase separate overnight. The water/salt layer was thenremoved, yielding the formylated hydroxy-terminated product of theformula

EXAMPLE II Acetylation/Protection

[0136] To a 1,000 milliliter flask equipped with a vacuum adapter andmagnetic stirrer was added about 200.0 grams of a random POE (3.5) POP(6.5) N-ethyl aniline, of the formula

[0137] wherein 3.5 represents the average number of repeatpolyoxyethylene units per molecule and 6.5 represents the average numberof repeat polyoxypropylene units per molecule, and wherein thepolyoxyethylene and polyoxypropylene units are randomly mixed within thepolyoxyalkylene chain (obtained as SO-7864 from Henkel Corp., Mauldin,S.C.). The flask was placed in a 140° C. oil bath under vacuum withstirring for about 1 hour. The vacuum source was then removed and about36.5 grams of acetic anhydride (obtained from Aldrich Chemical Co.,Milwaukee, Wis.) and 10 drops of 1-methylimidazole (obtained fromAldrich Chemical Co.) were added to the flask. A nitrogen atmosphere andreflux condenser were then introduced, and the mixture was allowed toheat at 130 to 135° C. for about 3 hours. Thereafter, a vacuum wasgradually applied with the temperature at about 130° C. to remove excessacetic acid (generated as a reaction byproduct) and acetic anhydride.Infrared spectroscopy showed that the OH band (3200-3600 cm⁻¹) in thePOE/POP N-ethyl aniline had disappeared in the product, and a carbonylband (1720-1770 cm⁻¹) had appeared in the product, indicating thesuccess of the acetylation reaction.

Formylation

[0138] About 195.0 grams of the acetylated product thus formed wastransferred to a 1,000 milliliter 4-necked flask equipped with a Truborestirrer, constant pressure addition funnel, nitrogen atmosphere, andthermometer. About 51.0 grams of dimethyl formamide (obtained fromAldrich Chemical Co.) was added to the acetylated product, stirring wasinitiated, and the mixture was cooled to about 0° C. About 63.8 grams ofPOCl₃ (obtained from Aldrich Chemical Co.) were added to the additionfunnel and added dropwise to the reaction mixture at a rate to keep thetemperature below 5° C. (about 3 hours). The reaction mixture was thenstirred for 0.5 additional hour at 5° C., set at room temperatureovernight, and then heated to 80° C. for about 2 hours. Thereafter,about 275 grams of deionized water was added and enough 50 percentsodium hydroxide solution in water (solid sodium hydroxide obtained fromAldrich Chemical Co.) was added slowly at a rate to keep the temperaturebelow 80° C. Upon addition of all of the sodium hydroxide solution, themixture was poured into a 1,000 milliliter separatory funnel and allowedto phase separate. The bottom layer (comprising salt and water) was thendrained and discarded.

Deacetylation/Deprotection

[0139] The acetylated and formylated product thus formed was thentransferred back into a 1,000 milliliter 4-necked flask equipped with aTEFLON® coated magnet on a stirring hot plate. About 70 grams of sodiumhydroxide and 23 grams of potassium hydroxide (obtained from AldrichChemical Co.) was dissolved in 400 milliliters of deionized water, andthe reaction mixture was heated to 100° C. and maintained at thattemperature for about 2 hours. The product mixture was then poured intoa 2,000 milliliter separatory funnel and allowed to phase separateovernight. The water/salt layer was then removed. The product layer wastransferred to a 2 liter beaker, 400 grams of deionized water wereadded, and the mixture was neutralized to a pH of about 7 with sulfuricacid (obtained from Aldrich Chemical Co.). The mixture was then heatedto about 70° C. and transferred back to the separatory funnel andallowed to separate overnight. The water/salt layer was discarded,yielding the formylated hydroxy-terminated product of the formula

[0140] The product was stripped of any remaining residual water on arotary evaporator. Infrared spectroscopy showed that the OH band(3200-3600 cm⁻¹) in the POE(3.5) POP (6.5) N-ethyl aniline was againpresent in the product, and a carbonyl band (1720-1770 cm⁻¹) of theformyl group was present in the product.

EXAMPLE III Monohydroxyl Triphenylmethane Polyoxyalkylene TPM VioletColorant

[0141] To a 100 milliliter 1-necked round bottom flask equipped with amagnetic stirrer was added 20.0 grams (about 0.029 moles) of thepara-formylated POE(3.5) POP(6.5) N-ethyl aniline adduct prepared inExample II, 8.85 grams of N,N-diethylaniline (obtained from AldrichChemical Co.), 0.6 grams of urea (obtained from Aldrich Chemical Co.),and 1.5 grams of concentrated H₂SO₄ (obtained from Aldrich ChemicalCo.). The flask was placed into a 100° C. oil bath, stirring wascommenced, and the mixture was allowed to heat/stir for 3 hours. After 3hours, 3.1 grams of benzoquinone (obtained from Aldrich Chemical Co.)and 2.0 grams of water were added to the reaction mixture andstirring/heating was continued for 2 hours, at which time the flask wasremoved from the heat and the violet liquid product was allowed to coolto room temperature. The product at this point was a viscous violetliquid consistent with the formula

EXAMPLE IV

[0142] The process of Example III is repeated except that the formylatedhydroxy-terminated product prepared as described in Example I is usedinstead of the formylated hydroxy-terminated product prepared asdescribed in Example II. It is believed that the resulting product willhave a structure similar to that of the colorant of Example III exceptthat the product will be of the formula

EXAMPLE V Reaction Product of Benzophenonetetracarboxylic Dianhydride,Octophenol Ethoxylate, and Violet TPM Monohydroxyl Colorant

[0143] To a 1,000 milliliter three-neck resin kettle equipped with aTrubore stirrer, N₂ inlet, and thermocouple-temperature controller isadded 150.0 grams (0.93 equivalents) of benzophenonetetracarboxylicdianhydride (available from Aldrich Chemical Co., Milwaukee, Wis.) and211.6 grams (0.83 equivalents) of IGEPAL CA-210 (octylphenol ethoxylate,available from Rhone-Poulenc Co., Cranbury, N.J. Note: TRITON X15octylphenol ethoxylate, available from Union Carbide Chemicals andPlastics Company Inc., Danbury, Conn., can be directly substituted forIGEPAL CA-210 in this reaction.). The reaction mixture is heated to 150°C. with stirring under nitrogen. After 1.0 hours at 150° C. thetemperature is increased to 170° C. and held at that temperature for 3.5hours. A violet monohydroxyl polyalkyleneoxy colorant (103.0 grams,0.098 equivalents) prepared as described in Example III is then addedand allowed to react for 3 hours. The final magenta colored resinproduct is then poured into aluminum molds and allowed to cool andharden.

EXAMPLE VI

[0144] The colored resin prepared in Example V (20.5 grams) is combinedwith 58.7 grams of stearyl stearamide wax (KEMAMIDE® S-180, availablefrom Crompton Corporation, Greenwich, Conn.), 20.5 grams of glycerolester of hydrogenated abietic [rosin] acid (KE-100, available fromArakawa Chemical Industries, Ltd.), and 0.2 gram of NAUGUARD® 445antioxidant (available from Uniroyal Chemical Co., Middlebury, Conn.).The ingredients are heated to 115° C. until molten, mixed, filteredthrough a disc filter, poured into sticks, and used to generate printsin a XEROX® PHASER 860 printer.

EXAMPLE VII Reaction Product of Octylphenol Ethoxylate, IsophoroneDiisocyanate, and Violet TPM Monohydroxyl Polyoxyalkylene Colorant

[0145] 525.0 grams (4.73 equivalents) of isophorone diisocyanate(available from Bayer Corp., Pittsburgh, Pa.) and 1.5 grams ofdibutyltindilaurate catalyst (available from Aldrich Chemical Co.,Milwaukee, Wis.), followed by 1,150 grams (4.52 equivalents) ofoctylphenol ethoxylate (IGEPAL CA-210 octylphenol ethoxylate, availablefrom Rhone-Poulenc Co., Cranbury, N.J.), are added to a 3,000 milliliterthree-neck resin kettle equipped with a Trubore stirrer, N₂ atmosphereinlet, and a thermocouple-temperature controller. The reaction mixtureis heated to 135° C. with stirring under nitrogen. After 2.0 hours at135° C., 216.0 grams (0.210 equivalents) of violet monohydroxylpolyoxyalkylene colorant prepared as described in Example III above areadded and the reaction mixture is heated for approximately 2 hours. Anadditional 11.0 grams (0.0433 equivalents) of octylphenol ethoxylate arethen added and the reaction mixture is heated at 150° C. forapproximately 2 hours. An FT-IR of the product is obtained to ensurethat all of the isocyanate (NCO) functionality has been consumed. Theabsence (disappearance) of a peak at about 2285 cm⁻¹ (NCO) and theappearance (or increase in magnitude) of peaks at about 1740-1680 cm⁻¹and about 1540-1530 cm⁻¹ corresponding to urethane frequencies are usedto confirm that the isocyanate has been consumed. The diurethanereaction product is then poured into aluminum molds and allowed to cooland harden.

EXAMPLE VIII

[0146] In a stainless steel beaker are combined 500 grams of stearylstearamide wax (KEMAMIDE® S-180, available from Crompton Corporation,Greenwich, Conn.), 125 grams of UNIREZ 2970 tetra-amide resin (availablefrom Union Camp, Wayne, N.J.), 208 grams of the colored resin preparedas described in Example VII, and 1.6 grams of NAUGUARD® 445 antioxidant(available from Uniroyal Chemical Co., Middlebury, Conn.). The materialsare melted together at a temperature of about 140° C. in an oven, thenblended by stirring in a temperature controlled mantle at about 115° C.for about 0.5 hour. After stirring, the resulting ink is filteredthrough a heated Mott apparatus (available from Mott Metallurgical)using #3 Whatman filter paper and a pressure of about 15 psi. Thefiltered phase change ink is then poured into molds, allowed to solidifyto form ink sticks, and used to generate prints in d XEROX® PHASER 860printer.

EXAMPLE IX Reaction Product of Styrene-Maleic Anhydride Polymer withNeodol 1-3 and Violet TPM Monohydroxyl Polyoxyalkylene Colorant

[0147] To a 500 milliliter three-neck resin kettle equipped with aTEFLON® coated magnet, oil bath, and condenser is added 14.0 grams(0.068 equivalents) of styrene-maleic anhydride polymer (SMA 1000,available from Atochem Inc., Malvern, Pa.), 15.9 grams (0.052equivalents) of an alcohol of the formula C₁₁H₂₂—O—(CH₂CH₂O)_(n)Hwherein n has an average value of 3 (NEODOL 1-3, available from ShellChemical Company, Houston, Tex.), 0.017 equivalents of a violetmonohydroxyl polyoxyalkylene colorant prepared as described in ExampleIII, about 250 grams of acetonitrile (available from Aldrich ChemicalCo., Milwaukee, Wis.), and 2 drops of 1-methylimidazole catalyst(available from Aldrich Chemical Co.). The reaction mixture is heatedwith stirring to reflux and held at that state for 2 days. After 2 days,the acetonitrile is removed by distillation. The violet viscous coloredproduct still in the flask is then placed in a vacuum oven to remove anyresidue of acetonitrile.

EXAMPLE X

[0148] To a 100 milliliter beaker equipped with magnetic stir was addedabout 8 grams of the violet material prepared as described in Example 1×and 35 milliliters of concentrated ammonia solution. Stirring wascontinued until all the solid material dissolved. About 2 milliliters ofthis aqueous solution was placed on the platen of a K-proofer and printswere made. The prints were allowed to dry and tested for washfastness.No bleeding of color was observed.

[0149] Other embodiments and modifications of the present invention mayoccur to those of ordinary skill in the art subsequent to a review ofthe information presented herein; these embodiments and modifications,as well as equivalents thereof, are also included within the scope ofthis invention.

[0150] The recited order of processing elements or sequences, or the useof numbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A colorant compound of the formula

wherein R, R₁, R₂. R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, Independently of the others, is on integer of 0, 1, 2, 3,or 4, n is on integer representing the number of carbon atoms in eachrepeat alkylene oxide unit x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said colorant has no more than one —OH, —SH, or primaryor secondary amino group per molecule.
 2. A colorant compositionaccording to claim 1 wherein R is an alkyl group with at least onecarbon atom and with no more than about 50 carbon atoms, an aryl groupwith at least about 5 carbon atoms and with no more than about 50 carbonatoms, an arylalkyl group with at least about 6 carbon atoms and with nomore than about 50 carbon atoms, or an alkylaryl group with at leastabout 6 carbon atoms and with no more than about 50 carbon atoms.
 3. Acolorant composition according to claim 1 wherein R is ethyl.
 4. Acolorant composition according to claim 1 wherein n is at least about 2and wherein n is no more than about
 18. 5. A colorant compositionaccording to claim 1 wherein n is no more than about
 4. 6. A colorantcomposition according to claim 1 wherein x is at least about 2 andwherein x is no more than about
 100. 7. A colorant composition accordingto claim 1 wherein x is at least about 5 and wherein x is no more thanabout
 20. 8. A colorant composition according to claim 1 wherein R′_(a),R′_(b), and R′_(c) each, independently of the others, is a fluorineatom, a chlorine atom, a bromine atom, an iodine atom, an alkyl groupwith at least one carbon atom and with no more than about 25 carbonatoms, an alkoxy group with at least one carbon atom and with no morethan about 25 carbon atoms, a nitrile group, a nitro group, an amidegroup of the formula

wherein R_(m) is a hydrogen atom, an alkyl group with at least 1 carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast 5 carbon atoms and with no more than about 50 carbon atoms, anarylalkyl group with at least about 6 carbon atoms and with no more thanabout 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms, or asulfonamide group of the formula

wherein R_(p) is a hydrogen atom, an alkyl group with at least 1 carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast 5 carbon atoms and with no more than about 50 carbon atoms, anarylalkyl group with at least about 6 carbon atoms and with no more thanabout 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms.
 9. A colorantcomposition according to claim 1 wherein R₁, R₂, R₃, and R₄ each,independently of the others, is an alkyl group with at least one carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast about 5 carbon atoms and with no more than about 50 carbon atoms,an arylalkyl group with at least about 6 carbon atoms and with no morethan about 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms.
 10. A colorantcomposition according to claim 1 of the formula


11. A colorant composition according to claim 1 of the formula


12. A compound comprising two or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b) and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an onion, and g is the charge on theanion, wherein said moieties each contain no —OH groups, —SH groups, orprimary or secondary amino groups, said moieties being linked by acentral atom or group of atoms or bonded to a polymer.
 13. A compoundaccording to claim 12 wherein the moieties are linked by a group ofatoms or bonded to a polymer which is derived from an isocyanate.
 14. Acompound which is the reaction product of a colorant compositionaccording to claim 1 and a monoisocyanate.
 15. A compound according toclaim 14 wherein the monoisocyanate is octodecylisocyanate;hexadecylisocyanate; octylisocyanate; butyl and t-butylisocyanate;cyclohexyl isocyanate; adamantyl isocyanate; ethylisocyanatoacetate;ethoxycarbonylisocyanate; phenylisocyanate; alphamethylbenzylisocyanate, 2-phenylcyclopropyl isocyanate; benzylisocyanate;2-ethylphenylisocyanate; benzoylisocyanate; meta andpara-tolylisocyanate; 2-, 3-, or 4-nitrophenylisocyanates;2-ethoxyphenyl isocyanate; 3-methoxyphenyl isocyanate;4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyante; or mixtures thereof.
 16. A compound accordingto claim 13 wherein the isocyanate is a diisocyanate.
 17. A compoundaccording to claim 16 wherein the diisocyanate is isophoronediisocyanate; toluene diisocyanate; diphenylmethane-4,4′-diisocyanate;hydrogenated diphenylmethane-4,4′-diisocyanate; tetra-methyl xylenediisocyanate; hexamethylene-1,6-diisocyanate;hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; cyclohexylene diisocyanate or an isomer thereof;a uretidione dimer of hexamethylene-1,6-diisocyanate; or mixturesthereof.
 18. A compound according to claim 13 wherein the isocyanate isa triisocyanate or a polyisocyanate.
 19. A compound according to claim12 wherein the moieties are bonded to a polymer.
 20. A compoundaccording to claim 19 wherein the polymer is a polyurethane.
 21. Acompound according to claim 19 wherein the polymer is an anhyhdridepolymer.
 22. A compound according to claim 21 wherein the anhydridepolymer is a polymer of a cyclic anhydride.
 23. A compound according toclaim 21 wherein the anhydride polymer is a polymer of an alkylsuccinicanhydride or an alkenylsuccinic anhydride.
 24. A compound according toclaim 21 wherein the anhydride polymer is a polymer of maleic anhydride,2,3-diphenylmaleic anhydride, trimellitic anhydride, 2-phenylglutaricanhydride, homophthalic anhydride, isatoic anhydride, n-methylisatoicanhydride, 5-chloroisatoic anhydride, phthalic anhydride,3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 4-methylphthalicanhydride, 4,4′-(hexafluoroisopropylidine)-diphthalic anhydride,3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,tetrachlorophthalic anhydride, tetrabromophthalic anhydride,3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,3-nitrophthalic anhydride, 4-nitrophthalic anhydride,1,2,4,5-benzenetetracarboxylic dianhydride, diphenic anhydride,1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic anhydride,4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride,3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride,4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride dipotassium salt1,4,5,8-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylic dianhydride,cis-1,2,3,6-tetrahydrophthalic anhydride,cis-5-norbornene-endo-2,3dicarboxylic anhydride,endo-bicyco(2,2,2)oct-5-ene-2,3dicarboxylic anhydride, cantharidin,methyl-5-norbornene-2,3-dicarboxylic anhydride,exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,bicyclo(2,2,2)octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, citraconicanhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylicanhydride, 3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,dichloromaleic anhydride,1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric anhydride,2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride,3-ethyl-3-methylglutaric anhydride, 3,3tetramethyleneglutaric anhydride,hexafluoroglutaric anhydride, 3,5-diacetyltetrahydropyran-2,4,6-trione,ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaaceticdianhydride, diglycolic anhydride, succinic anhydride, methylsuccinicanhydride, 2,2-dimethylsuccinic anhydride, isobuteneylsuccinicanhydride, 2-octen-1-ylsuccinic anhydride, octadecenylsuccinicanhydride, 3-oxabicyclo(3,1,0)hexane-2,4-dione,cis-1,2-cyclohexanedicarboxylic anhydride,trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalicanhydride, itaconic anhydride, 2-dodecen-1-ylsuccinic anhydride, ormixtures thereof.
 25. A compound according to claim 21 wherein theanhydride polymer is a copolymer of an anhydride with styrene,butadiene, methoxyvinylether, ethylene, alpha-olefins, or mixturesthereof.
 26. A compound according to claim 21 wherein the anhydridepolymer is poly(methyl vinyl ether-maleic acid), poly(acrylicacid-co-maleic acid), poly(vinyl chloride-co-vinyl-acetate-co-maleicacid), poly(ethylene-maleic anhydride), poly(maleicanhydride-1-octadecene), poly(styrene-co-maleic anhydride), poly(methylvinyl ether-maleic anhydride), poly(ethylene-co-ethyl acrylate-co-maleicanhydride), poly(ethylene-co-vinyl acetate)-graft-maleic anhydride,polyethylene-graft-maleic anhydride, or polypropylene-graft-maleicanhydride.
 27. A phase change ink comprising a phase change carrier anda colorant compound comprising one or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c) independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is on integer representing the number of carbon atoms in eachrepeat alkylene oxide unit x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein, when the colorant compound contains exactly one of themoieties, the moiety contains no more than one —OH, —SH, or primary orsecondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.
 28. Aphase change ink according to claim 27 wherein the colorant containsexactly one of the moieties.
 29. A phase change ink according to claim27 wherein the colorant contains more than one of the moieties.
 30. Aphase change ink according to claim 27 wherein the phase change inkcarrier comprises a monoamide, a tetra-amide, or a mixture thereof. 31.An ink composition according to claim 27 wherein the phase change inkcarrier comprises (a) stearyl stearamide, (b) a dimer acid basedtetra-amide that is the reaction product of dimer acid, ethylenediamine, and stearic acid, or (c) mixtures thereof.
 32. An inkcomposition according to claim 27 wherein the phase change ink carriercomprises (a) stearyl stearamide, (b) a dimer acid based tetra-amidethat is the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, or (c) mixturesthereof.
 33. An ink composition according to claim 32 wherein thecarboxylic acid has at least about 40 carbon atoms, and wherein thecarboxylic acid has no more than about 200 carbon atoms.
 34. An inkcomposition according to claim 27 wherein the phase change ink carriercomprises an isocyanate-derived material.
 35. An ink compositionaccording to claim 27 wherein the phase change ink carrier comprises aurethane isocyanate-derived material, a urea isocyanate-derivedmaterial, a urethane/urea isocyanate-derived material, or mixturesthereof.
 36. An ink composition according to claim 27 wherein the phasechange ink carrier comprises a mixture of one or more amides and one ormore isocyanate-derived materials.
 37. An ink composition according toclaim 27 wherein the phase change ink carrier comprises one or morematerials selected from paraffins, microcrystalline waxes, polyethylenewaxes, ester waxes, amide waxes, fatty acids, fatty alcohols, fattyamides, sulfonamide materials, tall oil rosins, rosin esters,ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers,ethylene/vinyl acetate/acrylic acid copolymers, copolymers of acrylicacid with polyamides, ionomers, and mixtures thereof.
 38. An inkcomposition according to claim 27 wherein the ink carrier comprises (a)a polyethylene wax, (b) a stearyl stearamide wax, (c) a dimer acid basedtetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms,(d) a urethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate, (e)a urethane resin that is the adduct of three equivalents of stearylisocyanate and a glycerol-based alcohol, and (f) an antioxidant.
 39. Anink composition according to claim 27 wherein the ink carrier comprises(a) a polyethylene wax in an amount of at least about 25 percent byweight of the ink and in an amount of no more than about 60 percent byweight of the ink, (b) a stearyl stearamide wax in an amount of at leastabout 8 percent by weight of the ink and in an amount of no more thanabout 32 percent by weight of the ink, (c) a dimer acid basedtetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms inan amount of at least about 10 percent by weight of the ink and in anamount of no more than about 32 percent by weight of the ink, (d) aurethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate in anamount of at least about 6 percent by weight of the ink and in an amountof no more than about 16 percent by weight of the ink, (e) a urethaneresin that is the adduct of three equivalents of stearyl isocyanate anda glycerol-based alcohol in an amount of at least about 2 percent byweight of the ink and in an amount of no more than about 13 percent byweight of the ink, and (f) an antioxidant in an amount of at least about0.01 percent by weight of the ink and in an amount of no more than about1 percent by weight of the ink.
 40. A process which comprises (1)incorporating into an ink jet printing apparatus a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound comprising one or more moieties of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein, when the colorant compound contains exactly one of themoieties, the moiety contains no more than one —OH, —SH, or primary orsecondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups: (2)melting the ink and (3) causing droplets of the melted ink to be ejectedin an imagewise pattern onto a substrate.
 41. A process according toclaim 40 wherein the substrate is a final recording sheet and dropletsof the melted ink are ejected in an imagewise pattern directly onto thefinal recording sheet.
 42. A process according to claim 40 wherein thesubstrate is an intermediate transfer member and droplets of the meltedink are ejected in an imagewise pattern onto the intermediate transfermember followed by transfer of the imagewise pattern from theintermediate transfer member to a final recording sheet.
 43. A processaccording to claim 42 wherein the intermediate transfer member is heatedto a temperature above that of the final recording sheet and below thatof the melted ink in the printing apparatus.
 44. A process according toclaim 40 wherein the printing apparatus employs a piezoelectric ink jetprocess, wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.